CN115806470A

CN115806470A - Process for preparing hydrogenated bisphenol A

Info

Publication number: CN115806470A
Application number: CN202211085500.0A
Authority: CN
Inventors: 卢奇润; 蒋正姬; 朴帝泳; 曺南显
Original assignee: Korea Kumho Petrochemical Co Ltd
Current assignee: Kumho Petrochemical Co Ltd
Priority date: 2021-09-15
Filing date: 2022-09-06
Publication date: 2023-03-17
Also published as: US20230084194A1; JP7405924B2; TW202313537A; JP2023043169A; EP4151613A1; WO2023042993A1; US11834395B2; KR20230039949A

Abstract

An embodiment of the present invention provides a method for preparing hydrogenated bisphenol a, comprising: step (a), heating a reactor in which bisphenol A, a solvent and a ruthenium supported catalyst are added; a step (b) of performing a reaction while supplying hydrogen gas to the reactor; and (c) performing a reaction after the supply of hydrogen is blocked.

Description

Process for preparing hydrogenated bisphenol A

Technical Field

The present specification relates to a process for the preparation of hydrogenated bisphenol a.

Background

Hydrogenated bisphenol A, 2-Bis (4-hydroxycyclohexyl) propane (2, 2-Bis (4-hydroxycyclohexyl) propane), is a useful material as a raw material for polymer polymerization. For example, polyester resins prepared by polycondensation of hydrogenated bisphenol a with dibasic acids such as phthalic acid, maleic acid and the like exhibit excellent heat resistance and moisture resistance. The epoxy resin prepared by reacting hydrogenated bisphenol A with epichlorohydrin has excellent electrical properties, contains no aromatic ring, has a small yellow discoloration, and thus can be used in places where weather resistance is required, and has excellent workability at low viscosity. In addition, due to the controversy of the harmfulness of bisphenol a, international demand for environmentally friendly products as a substitute for bisphenol a is increasing.

Many researchers have studied a method of hydrogenating aromatic rings of bisphenol a using a metal supported catalyst in order to prepare hydrogenated bisphenol a. It is reported that the yield and/or reaction rate of hydrogenated bisphenol a can be increased mainly by using an improved metal-supported catalyst or by using a specific reaction solvent. However, the conventional techniques still have problems in terms of cost of the catalyst, reaction yield of hydrogenated bisphenol a, reaction time, and the like, in terms of economical efficiency.

In addition, hydrogenated bisphenol A produced by hydrogenation of bisphenol A is generally classified into three stereoisomers, i.e., a mixture of cis/cis (cis/cis) isomer, cis/trans (cis/trans) isomer and trans/trans (trans/trans) isomer, according to the steric structure of two cyclohexanes linked by an isopropylidene group. Among the stereoisomers of hydrogenated bisphenol a, the trans/trans isomer structure is known to be the most stable. When hydrogenated bisphenol a having a high trans/trans isomer ratio is used, a polymer resin having excellent properties such as hardness and glass transition temperature can be polymerized, and therefore, it is necessary to develop a process for producing hydrogenated bisphenol a having a high trans/trans isomer ratio.

Disclosure of Invention

The matters described in the present specification are to solve the problems of the prior art described above, and an object of the present specification is to provide a process for producing hydrogenated bisphenol a with a high yield and a high trans/trans isomer ratio.

According to one aspect, there is provided a process for the preparation of hydrogenated bisphenol a comprising: step (a), heating a reactor in which bisphenol A, a solvent and a ruthenium-supported catalyst are added; a step (b) of performing a reaction while supplying hydrogen gas to the reactor; and (c) carrying out a reaction after the supply of hydrogen gas is blocked.

In one embodiment, in the step (b), the hydrogen gas may be supplied at a pressure of 30 to 60 bar.

In an embodiment, the step (b) may include: a step (b 1) of supplying hydrogen gas at a pressure of 30 to 45 bar in a reactor having an internal temperature of 90 to 120 ℃; and a step (b 2) of supplying hydrogen gas at a pressure of 45 to 60 bar in a reactor having an internal temperature of 120 to 160 ℃.

In one embodiment, the reaction time of step (b) may be 30 minutes to 180 minutes.

In one embodiment, the reaction temperature of the step (b) and the step (c) may be 120 ℃ to 160 ℃, respectively.

In one embodiment, the reaction pressure of the step (b) and the step (c) may be 30 bar to 60 bar, respectively.

In one embodiment, the reaction time of step (c) may be 30 minutes to 90 minutes.

In one embodiment, the hydrogenated bisphenol a content of the product of the step (c) may be 96% or more.

In one embodiment, the trans/trans isomer ratio of hydrogenated bisphenol A in the product of step (c) may be 45% or more.

According to an aspect of the present specification, hydrogenated bisphenol A having a high trans/trans isomer ratio can be produced in a high yield.

In addition, the method for producing hydrogenated bisphenol a according to another aspect of the present specification can be applied to an economical and environmentally friendly process because the reaction time is short and the catalyst can be reused.

The effects of the present invention are not limited to the above-described effects, and it should be understood that the effects include all the effects inferred from the configurations of the invention described in the detailed description of the present invention and claims.

Detailed Description

Hereinafter, one aspect of the present specification will be described. However, the matters described in the present specification can be realized in various forms, and are not limited to the embodiments described in the present specification.

Throughout the specification, when it is described that one component is "connected" to another component, it includes not only the case of "directly connected" but also the case of "connected with another component interposed therebetween". In addition, when a component is referred to as being "comprising" a component, it is intended to include the other component but not to exclude the other component unless the component is specifically referred to the contrary.

In this specification, when describing a range of numerical values, unless specifically stated otherwise, these values have the precision of the significant figures provided in accordance with standard rules in chemistry for significant figures. For example, 10 includes a range of 5.0 to 14.9, while the number 10.0 includes a range of 9.50 to 10.49.

The term "Bisphenol A (BPA)" as used in the present specification means 2,2-Bis (4-hydroxyphenyl) propane (2, 2-Bis (4-hydroxyphenyl) propane).

The term "Hydrogenated Bisphenol A (HBPA)" as used herein means 2,2-Bis (4-hydroxycyclohexyl) propane (2, 2-Bis (4-hydroxycyclohexyl) propane).

Hereinafter, an embodiment according to the present specification is described in detail.

A method of preparing hydrogenated bisphenol a according to one aspect of the present description comprises: step (a), heating a reactor in which bisphenol A, a solvent and a ruthenium supported catalyst are added; a step (b) of performing a reaction while supplying hydrogen gas to the reactor; and (c) performing a reaction after the supply of hydrogen is blocked.

The step (a) is a step of adding bisphenol a, a solvent and a ruthenium-supported catalyst as raw materials to a reactor and heating the reactor to raise the temperature inside the reactor to prepare for a reaction.

As the above solvent, any kind of solvent capable of dissolving bisphenol a may be used, for example, an alcohol solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, and a combination of two or more thereof may be used, but is not limited thereto.

When the above ruthenium-supported catalyst is applied to the above preparation method, the above ruthenium-supported catalyst can be reused 20 times or more in the hydrogenated bisphenol a preparation process without additional input of the catalyst and without delay of the reaction time. Even if the above-mentioned catalyst is repeatedly used, a high yield of hydrogenated bisphenol a and a high ratio of hydrogenated bisphenol a trans/trans isomers in the product can be maintained by the method for producing hydrogenated bisphenol a according to an embodiment of the present specification. By virtue of the high reusability of the catalyst, the process economy can be improved, and an environment-friendly process design can be carried out.

The above catalyst may be a catalyst in which ruthenium is supported on a carrier such as diatomaceous earth, pumice, activated carbon, silica gel, alumina, zirconia, titania, etc., and for example, may be a Ru/C catalyst in which ruthenium is supported on a carbon-based carrier, but is not limited thereto.

The ruthenium content in the above catalyst may be 0.1 to 20% by weight, based on the total weight of the catalyst. For example, the ruthenium content can be 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, or a range therebetween.

The content of the above catalyst may be 0.5 to 10 parts by weight based on 100 parts by weight of the above bisphenol a. For example, the content of the above catalyst may be 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or a range therebetween, but is not limited thereto. If the content of the above catalyst is outside the above range, the reaction time may be increased to lower the process efficiency, and the ratio of hydrogenated bisphenol A trans/trans isomers in the final product may be decreased.

The step (b) is a step of performing a hydrogenation reaction, i.e., a hydrogen addition reaction, and is a step of supplying hydrogen gas into the reactor and simultaneously performing a reaction to hydrogenate the aromatic ring of bisphenol a as a raw material.

In the step (b), the hydrogen may be supplied at a pressure of 30 to 60 bar. For example, the pressure may be 30 bar, 32 bar, 34 bar, 36 bar, 38 bar, 40 bar, 42 bar, 44 bar, 46 bar, 48 bar, 50 bar, 52 bar, 54 bar, 56 bar, 58 bar, 60 bar or a range therebetween. When the supply pressure of the above-mentioned hydrogen gas is out of the above-mentioned range, the yield of hydrogenated bisphenol A may be lowered.

The step (b) may include: a step (b 1) of supplying hydrogen gas at a pressure of 30 to 45 bar in a reactor having an internal temperature of 90 to 120 ℃; and a step (b 2) of supplying hydrogen gas at a pressure of 45 to 60 bar in a reactor having an internal temperature of 120 to 160 ℃. The yield of hydrogenated bisphenol A can be improved by adjusting the supply pressure of hydrogen gas in accordance with the temperature change in the reactor.

The reaction time of the above step (b) may be 30 minutes to 180 minutes. For example, the reaction time can be 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, or a range therebetween. If the reaction time is shorter than the above range, the hydrogenation reaction may not be sufficiently performed, the yield of hydrogenated bisphenol A may be rapidly decreased, and if the reaction time is longer than the above range, the process efficiency and the economy may be deteriorated.

The step (c) is a step of carrying out an additional reaction after the supply of hydrogen gas in the step (b) is interrupted to obtain a product, and the ratio of hydrogenated bisphenol A trans/trans isomer in the product can be increased by carrying out the additional reaction after the supply of hydrogen gas is interrupted.

The reaction temperature in the above step (b) and the above step (c) may be 120 ℃ to 160 ℃, respectively. For example, the reaction temperature can be 120 degrees, 125 degrees, 130 degrees, 135 degrees, 140 degrees, 145 degrees, 150 degrees, 155 degrees, 160 degrees or two value ranges. If the reaction temperature is lower than the above range, the yield of hydrogenated bisphenol A and the trans/trans isomer ratio of hydrogenated bisphenol A in the product may decrease, and if the reaction temperature is higher than the above range, the yield of hydrogenated bisphenol A may decrease and the production of impurities may increase.

The reaction temperature in the above step (b) and the reaction temperature in the above step (c) may be the same as or different from each other.

The reaction pressure in the above step (b) and the above step (c) may be 30 to 60 bar, respectively. For example, the reaction pressure may be 30 bar, 32 bar, 34 bar, 36 bar, 38 bar, 40 bar, 42 bar, 44 bar, 46 bar, 48 bar, 50 bar, 52 bar, 54 bar, 56 bar, 58 bar, 60 bar or a range therebetween, and the reaction pressure of the step (b) and the reaction pressure of the step (c) may be the same as or different from each other.

The reaction time of the above step (c) may be 30 minutes to 90 minutes. For example, the reaction time may be 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, or a range therebetween. If the reaction time in the above step (c) is shorter than the above range, the yield of hydrogenated bisphenol A and the trans/trans isomer ratio of hydrogenated bisphenol A in the product may be lowered, and if the reaction temperature is longer than the above range, the process efficiency and economy may be lowered.

The total reaction time of the above step (b) and the above step (c) may be 90 minutes to 240 minutes. For example, the reaction time may be 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, 190 minutes, 200 minutes, 210 minutes, 220 minutes, 230 minutes, 240 minutes, or a range therebetween. The method for preparing hydrogenated bisphenol a according to one embodiment of the present specification has a shorter reaction time compared to the prior art, and thus can improve process efficiency.

The method for producing hydrogenated bisphenol a according to one embodiment of the present specification improves the yield of hydrogenated bisphenol a and the trans/trans isomer ratio of hydrogenated bisphenol a in the product by performing an additional reaction after blocking hydrogen supply, and at the same time, shortens the reaction time as compared to the prior art, thereby improving process efficiency and economy.

The hydrogenated bisphenol A content of the product of the step (c) may be 96% or more. For example, the ratio of the hydrogenated bisphenol a may be 96% or more, 96.5% or more, 97% or more, 97.5% or more, 98% or more, 98.5% or more, 99% or more, or 99.5% or more.

The hydrogenated bisphenol A in the product of step (c) above may be a mixture of cis/cis, cis/trans and trans/trans isomers, the trans/trans isomer content of the three isomers being the highest possible.

The trans/trans isomer ratio of the hydrogenated bisphenol A in the product of the step (c) may be 45% or more. For example, the ratio of the trans/trans isomer may be 45% or more, 46% or more, 47% or more, 48% or more, 49% or more, 50% or more, 51% or more, 52% or more, 53% or more, 54% or more, or 55% or more. The hydrogenated bisphenol a prepared by the method of preparing hydrogenated bisphenol a according to an embodiment of the present disclosure has a high trans/trans isomer ratio, and thus when applied to a polymerization process of a polymer resin, the properties such as hardness and glass transition temperature of the polymer resin can be improved.

The hydrogenated bisphenol a intermediate in the product of the step (c) may be present in a ratio of 1.0% or less. For example, the ratio of the intermediate product may be 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less.

The above-mentioned process for producing hydrogenated bisphenol A may further comprise a step (d) of purifying the product of the above-mentioned step (c) to obtain hydrogenated bisphenol A.

The step (d) may be performed by a distillation process after reducing the temperature of the reactor after completion of the reaction, and the purity of the hydrogenated bisphenol a after purification in the step (d) may be 97% or more. For example, the purity of the hydrogenated bisphenol A may be 97% or more, 97.5% or more, 98% or more, 98.5% or more, 99% or more, or 99.5% or more.

Hereinafter, embodiments of the present specification will be described in more detail. However, the following experimental results are merely representative experimental results in the above examples, and the examples and the like should not be construed to limit or restrict the scope and content of the present specification. Effects of various embodiments of the present specification, which are not explicitly presented hereinafter, are specifically described in the respective sections.

Example 1

After 500g of Bisphenol A (Bisphenol A, BPA), 1000g of Isopropanol (IPA) and 15g of 5% Ru/C catalyst were fed to the hydrogenation reactor, the nitrogen gas was replaced 3 times by an internal pressure of 4 bar inside the hydrogenation reactor. The internal temperature was raised by supplying steam as a heat source while stirring the above hydrogenation reactor. When the temperature inside the reactor reached 100 ℃, hydrogen gas was fed at an internal pressure of 40 bar, and when the temperature inside the reactor reached 150 ℃, hydrogen gas was fed at an internal pressure of 52 bar. The hydrogenation reaction was carried out for 60 minutes while maintaining the reaction temperature at 150. + -. 2 ℃ and then hydrogen supply was blocked. After an additional reaction at a reaction temperature of 150 ℃ and a reaction pressure of 50 bar for 40 minutes or more with hydrogen supply interrupted, the product was sampled every 10 minutes using a sampling port of the hydrogenation reactor and analyzed by Gas Chromatography (GC). As a result of the gas chromatography analysis, when the content of trans/trans isomer of Hydrogenated Bisphenol a (HBPA) was 52% or more and the content of Hydrogenated Bisphenol a intermediate product was 0.5% or less, the reaction was terminated, the internal temperature of the reactor was lowered to 100 ℃, and then the by-product was separated by a distillation process to obtain Hydrogenated Bisphenol a.

The results of gas chromatographic analysis based on the additional reaction time under the above-described hydrogen supply blocking are summarized in table 1 below.

TABLE 1

As is clear from Table 1 above, the yield of hydrogenated bisphenol A and the trans/trans isomer content of hydrogenated bisphenol A increase as the additional reaction time under hydrogen supply inhibition is longer. In particular, the content of trans/trans isomer rapidly increased in comparison with the yield of hydrogenated bisphenol A with the increase of the reaction time, and as a result, in the case of the product subjected to the additional reaction for 70 minutes, the yield of hydrogenated bisphenol A was the highest at 97.08%, and the content of hydrogenated bisphenol A trans/trans isomer was also the highest at 54.88%.

Example 2

After 500g of bisphenol A, 1000g of isopropanol and 15g of 5% Ru/C catalyst were fed to the hydrogenation reactor, nitrogen gas was replaced with 4 bar internal pressure inside the hydrogenation reactor 3 times. The internal temperature was raised by supplying steam as a heat source while stirring the above hydrogenation reactor. When the temperature inside the reactor reached 100 ℃, hydrogen gas was fed at an internal pressure of 40 bar, and when the temperature inside the reactor reached 140 ℃, hydrogen gas was fed at an internal pressure of 52 bar. The hydrogenation reaction was carried out for 60 minutes while maintaining the reaction temperature at 140. + -. 2 ℃ and then hydrogen supply was blocked. An additional reaction was carried out for 70 minutes at a reaction temperature of 140 ℃ and a reaction pressure of 50 bar with hydrogen supply interrupted. And (3) after carrying out gas chromatography analysis on a product sampled by using a sampling port of the hydrogenation reactor, stopping the reaction, reducing the internal temperature of the reactor to 100 ℃, and separating a byproduct by a distillation process to obtain the hydrogenated bisphenol A.

Example 3

After 500g of bisphenol A, 1000g of isopropanol and 15g of 5% Ru/C catalyst were fed to the hydrogenation reactor, nitrogen gas was replaced with 4 bar internal pressure inside the hydrogenation reactor 3 times. The internal temperature was raised by supplying steam as a heat source while stirring the above hydrogenation reactor. When the temperature inside the reactor reached 100 ℃, hydrogen was fed at an internal pressure of 40 bar, and when the temperature inside the reactor reached 130 ℃, hydrogen was fed at an internal pressure of 52 bar. The hydrogenation reaction was carried out for 60 minutes while maintaining the reaction temperature at 130. + -. 2 ℃ and then hydrogen supply was blocked. An additional reaction was carried out for 70 minutes at a reaction temperature of 130 ℃ and a reaction pressure of 50 bar with hydrogen supply blocked. And (3) after carrying out gas chromatography analysis on a product sampled by using a sampling port of the hydrogenation reactor, stopping the reaction, reducing the internal temperature of the reactor to 100 ℃, and separating a byproduct by a distillation process to obtain the hydrogenated bisphenol A.

In the above examples 1 to 3, the results of gas chromatography analysis of the products obtained after the additional reaction was carried out for 70 minutes are summarized in the following table 2.

TABLE 2

Referring to Table 2 above, the higher the reaction temperature, the higher the content of the hydrogenated bisphenol A trans/trans isomer, and accordingly, the product of example 1, which was reacted at 150 ℃, had the highest hydrogenated bisphenol A trans/trans isomer ratio of 54.88%.

Examples of the experiments

In order to evaluate the reusability of the 5-percent Ru/C catalyst used in examples 1 to 3 above, the process for producing hydrogenated bisphenol A was repeated 20 times in the same manner as in example 1 above without adding an additional catalyst.

As a result, it was confirmed that the average yield of hydrogenated bisphenol A at 20 times was 96.61%, the average content of hydrogenated bisphenol A trans/trans isomer at 20 times was 52.5%, and the yield of hydrogenated bisphenol A and the content of hydrogenated bisphenol A trans/trans isomer were constant, whereby the catalyst was excellent in reusability without delay of the reaction time.

The above description of the present specification is merely exemplary, and it will be understood by those skilled in the art to which the present specification pertains that the present specification can be easily modified into other specific forms without changing the technical ideas or essential features of the present specification. Therefore, it should be understood that the above-described embodiments are merely illustrative in all respects, and not restrictive. For example, the components described as a single type may be implemented as a dispersion, and similarly, the components described as a dispersion may be implemented in a combined form.

The scope of the present specification is indicated by the appended claims, and all changes and modifications derived from the meaning and range of claims and their equivalents are intended to be interpreted as being included in the scope of the present specification.

Claims

1. A process for the preparation of hydrogenated bisphenol a comprising:

heating a reactor in which bisphenol A, a solvent and a ruthenium-supported catalyst are added;

a step (b) of performing a reaction while supplying hydrogen gas to the reactor; and

and (c) performing a reaction after blocking the supply of hydrogen.

2. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

in the step (b), the hydrogen gas is supplied at a pressure of 30 to 60 bar.

3. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the step (b) includes:

a step (b 1) of supplying hydrogen gas at a pressure of 30 to 45 bar in a reactor having an internal temperature of 90 to 120 ℃; and

step (b 2) of supplying hydrogen gas at a pressure of 45 to 60 bar in a reactor having an internal temperature of 120 to 160 ℃.

4. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the reaction time of the above step (b) is 30 to 180 minutes.

5. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the reaction temperatures in the above step (b) and the above step (c) are 120 ℃ to 160 ℃, respectively.

6. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the reaction pressure in the above step (b) and the above step (c) is 30 to 60 bar, respectively.

7. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the reaction time in the above step (c) is 30 to 90 minutes.

8. The process for producing hydrogenated bisphenol A according to claim 1,

the hydrogenated bisphenol A content of the product of the step (c) is 96% or more.

9. The process for producing hydrogenated bisphenol A according to claim 1, wherein,

the trans/trans isomer ratio of the hydrogenated bisphenol A in the product of the step (c) is 45% or more.